CN117417492A - Organic fluorine-silicon modified acrylic resin and preparation method thereof - Google Patents
Organic fluorine-silicon modified acrylic resin and preparation method thereof Download PDFInfo
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- CN117417492A CN117417492A CN202311557679.XA CN202311557679A CN117417492A CN 117417492 A CN117417492 A CN 117417492A CN 202311557679 A CN202311557679 A CN 202311557679A CN 117417492 A CN117417492 A CN 117417492A
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Abstract
The invention relates to the technical field of polymer coating, and discloses an organic fluorine-silicon modified acrylic resin and a preparation method thereof, wherein the organic fluorine-silicon modified acrylic resin comprises fluorine-silicon active intermediate sol, methacrylate unsaturated monomer, acrylate monomer and initiator; the preparation method of the fluorine-silicon active intermediate sol comprises the following steps: mixing vinyl alkoxy silane, 1, 2-bis trimethoxy silicon-based ethane and fluorine-containing alkyl alkoxy silane, dissolving in alcohol solution, stirring and heating; and (3) dropwise adding an acid catalyst, heating, preserving heat, reacting for 1-5h, and removing the alcohol solution to obtain fluorine-silicon active intermediate sol. The organic fluorine-silicon modified acrylic resin prepared by carrying out chemical modification treatment on the acrylic ester monomer through the specific fluorine-silicon intermediate prepared by the invention has good water resistance, strong heat resistance and strong aging resistance in a high-temperature environment.
Description
Technical Field
The invention relates to the technical field of polymer coatings, in particular to an organic fluorine-silicon modified acrylic resin and a preparation method thereof.
Background
The polymer coating is a liquid material formed by optimally combining synthetic high-molecular polymer emulsion and various additives, and is a material which has high elasticity of the synthetic high-molecular polymer material and good durability of inorganic materials. The common polymer coating is mostly prepared from raw materials such as polyacrylate, modified polyacrylate high polymer resin and the like, and the acrylic resin has good weather resistance, high hardness and high glossiness, and can be matched with various polymers such as amino resin, polyurethane resin, epoxy resin and the like for use to prepare a coating system with balanced comprehensive properties.
However, the conventional polyacrylate resins have the following problems:
(1) Poor hydrophobicity: the coating made of the traditional polyacrylate resin has higher surface energy, and the static contact angle with water is usually smaller than 90 degrees, namely the water resistance and the anti-fouling performance of the coating are poor.
(2) Poor heat resistance and stability: the traditional polyacrylic resin takes a C-C structure as a main chain, a side chain contains a large amount of C-H alkyl groups, and is limited by the structural characteristics of the C-H side chain, so that the polyacrylate resin is difficult to adapt to harsh use environments in the aspects of heat resistance and ultraviolet light resistance stability.
(3) The preparation process is complicated: chain initiation is usually carried out by adopting a mode of generating free radicals by peroxide thermal decomposition, the reaction temperature varies with the peroxide thermal decomposition temperature, but the reaction temperature is higher as a whole, the heat release amount is large, a process of gradually dropwise adding monomers is needed, namely, the reaction time is long, the production efficiency is low, and the quality stability among different batches of products is poor.
The organic silicon resin is a polymer with skeleton comprising silicon atoms and oxygen atoms connected alternately, and different organic groups are connected with the silicon atoms, and the molecular structure of the polymer contains both organic groups and inorganic structures, and the special composition and molecular structure can make the polymer gather the functional characteristics of organic matters and inorganic matters at the same time. The silicone resin contains a large amount of Si-O-Si structures in the molecule, since the bond energy of Si-O bonds is significantly larger than that of C-O bonds, the silicone resin exhibits a significant advantage in heat resistance.
Therefore, technical means for modifying polyacrylate resin by adopting organosilicon are proposed so as to improve the material performance. As disclosed in the patent publication No. CN116903803a, an application of organosilicon modified acrylic resin nanoparticles in preparing photo-curing resin by UV photo-curing is disclosed, wherein an organopolysiloxane core emulsion is thermally initiated to modify acrylate monomers to prepare organosilicon modified acrylic resin nanoparticles, and the organosilicon modified acrylic resin nanoparticles are added into UV photosensitive resin liquid in the form of powder.
However, the existing polyacrylate resin cannot achieve improvement of comprehensive properties of water resistance, heat resistance, stability and the like at the same time, namely, the comprehensive properties of the polyacrylate resin are poor.
Disclosure of Invention
The invention aims to solve the technical problems that:
at present, in order to improve the material performance of polyacrylate resin, a technical means for improving the acrylic acid ester by adopting an organosilicon material is proposed so as to endow the organosilicon with good heat resistance. However, the existing modified polyacrylate resin cannot achieve improvement of comprehensive properties such as water resistance, heat resistance and stability, namely the comprehensive properties of the polyacrylate resin are poor, so that the application range of the polyacrylate resin is narrow, and high requirements are placed on the use environment.
The invention adopts the technical scheme that:
the invention provides an organic fluorine-silicon modified acrylic resin, which comprises fluorine-silicon active intermediate sol, methacrylate unsaturated monomer, acrylate monomer and initiator;
the preparation method of the fluorine-silicon active intermediate sol comprises the following steps:
mixing vinyl alkoxy silane, 1, 2-bis trimethoxy silicon-based ethane and fluorine-containing alkyl alkoxy silane, dissolving in alcohol solution, stirring and heating; and (3) dropwise adding an acid catalyst, heating, preserving heat, reacting for 1-5h, and removing the alcohol solution to obtain fluorine-silicon active intermediate sol.
Preferably, the fluorine-silicon active intermediate sol is prepared from 5-20 parts of vinyl alkoxy silane, 0.5-2 parts of 1, 2-bis trimethoxy silicon-based ethane and 1-10 parts of fluorine-containing alkyl alkoxy silane by mass.
Preferably, the alcohol solution is used in an amount of 63.6 to 85.8 parts by mass, and 30 to 50 parts by mass of the alcohol solution is removed after the reaction.
Preferably, the amount of the acid catalyst is 1 to 5 parts by mass, and 3 to 10 parts of water is also dropped when the acid catalyst is dropped.
Preferably, after dissolution in an alcohol solution, heating to 40-50 ℃; after dropping the acid catalyst, heating to 50-60 ℃.
Preferably, the fluorine-silicon reactive intermediate sol comprises 3-10 parts by mass, 10-30 parts by mass of methacrylate unsaturated monomer, 10-40 parts by mass of acrylate monomer and 1-3 parts by mass of initiator.
The preparation method of the organic fluorine silicon modified acrylic resin comprises the following steps:
s1, preparing a pre-reaction liquid:
mixing fluorine-silicon active intermediate sol with methacrylate unsaturated monomer, acrylate monomer, initiator and solvent, and stirring in a constant-temperature water bath to obtain a pre-reaction solution;
s2, preparing organic fluorine-silicon modified acrylic resin:
and (3) placing the pre-reaction liquid under the illumination with the wavelength of 350-380nm for reaction, and diluting to obtain the organic fluorosilicone modified acrylic resin.
Preferably, in the step S1, the constant temperature water bath temperature is 25-40 ℃, and the stirring time is 5-15min.
Preferably, in the step S2, the reaction flow rate of the pre-reaction liquid is controlled to be 10-20mL/min, and the reaction temperature is controlled to be 25-40 ℃.
Preferably, in step S1, the solvent is used in an amount of 24 to 54 parts by mass; in step S2, 80-100 parts of solvent is used.
The beneficial effects of the invention are as follows:
in the fluoropolymer, the polymer is composed ofHas extremely low critical surface tension at the C-F bond, wherein-CF 3 The critical surface tension of the group is far smaller than that of other common alkyl groups, and the perfluorinated side chains in the fluorine-containing polymer are oriented outwards to form shielding protection for chains and internal molecules, so that the fluorine-containing polymer can be endowed with excellent performances such as good chemical inertness, weather resistance, stain resistance, water resistance, oil resistance, ultraviolet resistance and the like.
According to the organic fluorine-silicon modified acrylic resin and the preparation method thereof, on the basis of modification treatment of an organic silicon material on the acrylic resin, fluorine-containing polymers, namely the specific fluorine-silicon intermediate prepared by the preparation method, are further combined, and acrylate monomers are subjected to chemical modification treatment, so that the organic fluorine-silicon modified acrylic resin is finally prepared, and has the excellent performances of good water resistance, strong heat resistance and strong ageing resistance in a high-temperature environment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a preparation method of organic fluorine silicon modified acrylic resin, which comprises the following steps:
(1) Preparing fluorine-silicon active intermediate sol:
weighing 5-20 parts by weight of vinyl alkoxy silane, 0.5-2 parts by weight of 1, 2-bis trimethoxy silicon-based ethane and 1-10 parts by weight of fluorine-containing alkyl alkoxy silane, mixing, dissolving in 63.6-85.8 parts by weight of alcohol solution, stirring and heating; then 1-5 parts of acid catalyst and 3-10 parts of water are added dropwise, heating is continued, heat preservation is carried out for 1-5 hours, hydrolysis and copolymerization reaction are carried out, reduced pressure distillation is carried out, and partial solvent is removed, so that fluorine-silicon active intermediate sol containing vinyl in molecules is obtained;
(2) Preparing a pre-reaction liquid:
weighing 3-10 parts by mass of the fluorine-silicon active intermediate sol, 10-30 parts by mass of methacrylate unsaturated monomer, 10-40 parts by mass of acrylate monomer, 1-3 parts by mass of initiator and 24-54 parts by mass of solvent, and stirring in a constant-temperature water bath to obtain a mixed pre-reaction solution;
(3) Preparing organic fluorine silicon modified acrylic resin:
and (3) conveying the pre-reaction liquid into a photoreactor through a peristaltic pump, controlling the conveying flow to be 10-20mL/min, reacting at the reaction temperature of 25-40 ℃ under the illumination of 350-380nm wavelength, and diluting with a solvent to obtain the organic fluorosilicone modified acrylic resin.
Wherein, the vinyl alkoxy silane can be selected from one or more of vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl diethoxy silane and the like;
the fluorine-containing hydrocarbon alkoxy silane can be selected from 1H, 2H-perfluoro heptadecane trimethoxy silane, 1H, 2H-perfluoro heptadecane triethoxy silane one or more of 1h,2 h-perfluorooctyltrimethoxysilane, 1h,2 h-perfluorooctyltriethoxysilane, and the like;
the alcohol solution can be one or more selected from methanol, ethanol, isopropanol, n-butanol, isobutanol, propylene glycol monomethyl ether, etc.;
the acid catalyst can be one or more selected from glacial acetic acid, 36% hydrochloric acid, methanesulfonic acid and the like;
the methacrylate unsaturated monomer can be one or more selected from methyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, isobornyl methacrylate and the like;
the acrylic ester monomer can be selected from one or more of butyl acrylate, isooctyl acrylate, hydroxyethyl acrylate and the like;
the initiator can be selected from one or more of common photoinitiators such as 2-methyl-1-phenyl-2-propanol, a-ketoglutaric acid and the like;
the solvent can be one or more selected from 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, ethyl acetate, butyl acetate, etc.
In the invention, in the process of photoinitiation reaction, an initiator is decomposed to generate free radicals, so that the fluorine-silicon active intermediate sol and a methacrylate unsaturated monomer are initiated to generate free radical copolymerization reaction, and the fluorine-silicon modified polyacrylate polymer with a certain molecular weight is produced. The fluorine-silicon active intermediate sol is introduced, so that the surface energy of the modified polyacrylate polymer can be reduced, the surface hydrophobicity, the pollution resistance, the heat resistance and the ageing resistance of the material are improved, the free radical copolymerization reaction is easy to occur, the reaction process is fast, the preparation time can be effectively shortened, and the production efficiency is improved.
< example >
Example 1
(1) According to mass, 20 parts of vinyl trimethoxy silane, 0.5 part of 1, 2-bis trimethoxy silicon-based ethane, 1 part of 1H, 2H-perfluoro heptadecane trimethoxy silane, 63.6 parts of absolute ethyl alcohol, 5 parts of glacial acetic acid and 10 parts of deionized water are respectively measured;
mixing vinyl trimethoxy silane, 1, 2-bis trimethoxy silyl ethane and 1H, 2H-perfluoro heptadecane trimethoxy silane, adding into a reaction bottle filled with absolute ethyl alcohol, stirring, and heating to 50 ℃; then glacial acetic acid and deionized water are dripped at a constant speed, dripping is completed within 30min, heating is continued to be carried out, and the temperature is kept for 2h; vacuum distilling to remove about 30 parts of ethanol to obtain fluorine-silicon active intermediate sol A;
(2) In addition, 3 parts by mass of the fluorine-silicon active intermediate sol A, 30 parts by mass of methyl methacrylate, 5 parts by mass of butyl acrylate, 5 parts by mass of hydroxyethyl acrylate, 154 parts by mass of ethyl acetate and 3 parts by mass of 2-methyl-1-phenyl-2-propanol are respectively measured;
mixing fluorine-silicon active intermediate sol A, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, 54 parts of ethyl acetate and 2-methyl-1-phenyl-2-propanol, and placing the mixture in a water bath at 25 ℃ for constant temperature stirring for 10min to obtain a pre-reaction liquid;
conveying the pre-reaction liquid into an ultraviolet light reactor through a peristaltic pump, controlling the conveying flow to be 10mL/min, and controlling the reaction temperature to be 32 ℃ and the ultraviolet light irradiation wavelength to be 365nm; and collecting the reacted polymer solution at the outlet of the ultraviolet light reactor, adding the polymer solution into 100 parts of ethyl acetate, and mixing and diluting to obtain the organic fluorosilicone modified acrylic resin.
Example 2
(1) According to mass, 5 parts of vinyl trimethoxy silane, 0.5 part of 1, 2-bis trimethoxy silicon-based ethane, 5 parts of 1H, 2H-perfluoro heptadecane trimethoxy silane, 35.5 parts of methanol, 50 parts of absolute ethyl alcohol, 1 part of 36% hydrochloric acid and 3 parts of deionized water are respectively measured;
mixing vinyl trimethoxy silane, 1, 2-bis trimethoxy silyl ethane and 1H, 2H-perfluoro heptadecane trimethoxy silane, adding into a reaction bottle filled with a mixed solution of methanol and absolute ethanol, stirring, and heating to 50 ℃; then 36 percent hydrochloric acid and deionized water are dripped at a constant speed, the dripping is completed within 30 minutes, and the temperature is kept at 50 ℃ for 2 hours; vacuum distilling to remove about 30 parts of methanol to obtain fluorine-silicon active intermediate sol B;
(2) In addition, 3 parts of the fluorine-silicon active intermediate sol B, 10 parts of methyl methacrylate, 10 parts of butyl methacrylate, 10 parts of hydroxyethyl methacrylate, 40 parts of butyl acrylate, 24 parts of ethyl acetate, 100 parts of 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether and 3 parts of 2-methyl-1-phenyl-2-propanol are respectively measured according to mass;
mixing fluorine-silicon active intermediate sol B, methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, butyl acetate and 2-methyl-1-phenyl-2-propanol, and placing the mixture in a water bath at 30 ℃ for constant temperature stirring for 10min to obtain a pre-reaction liquid;
conveying the pre-reaction liquid into an ultraviolet light reactor through a peristaltic pump, controlling the conveying flow to be 20mL/min, and controlling the reaction temperature to be 32 ℃ and the ultraviolet light irradiation wavelength to be 365nm; and collecting the reacted polymer solution at the outlet of the ultraviolet light reactor, adding the polymer solution into 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, mixing and diluting to obtain the organic fluorosilicone modified acrylic resin.
Example 3
(1) According to mass, 2 parts of vinyl triethoxysilane, 2 parts of vinyl methyl diethoxysilane, 2 parts of 1, 2-bis trimethoxy silicon-based ethane, 5 parts of 1H, 2H-perfluoro heptadecane triethoxysilane, 85.5 parts of isopropanol, 1 part of 36% hydrochloric acid and 3 parts of deionized water are respectively measured;
mixing vinyl triethoxysilane, vinyl methyl diethoxysilane, 1, 2-bis trimethoxy silyl ethane, and 1H, 2H-perfluoro heptadecane triethoxysilane, adding into a reaction bottle filled with isopropanol, stirring, and heating to 50deg.C; then 36 percent hydrochloric acid and deionized water are dripped at a constant speed, dripping is completed within 30 minutes, heating is continued to be carried out, and the temperature is kept for 2 hours; distilling under reduced pressure to remove about 30 parts of isopropanol to obtain fluorine-silicon active intermediate sol C;
(2) In addition, according to mass, 10 parts of fluorine-silicon active intermediate sol C, 30 parts of isobornyl methacrylate, 30 parts of isooctyl acrylate, 27 parts of ethyl acetate, 100 parts of 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, 1 part of 2-methyl-1-phenyl-2-propanol and 2 parts of a-ketoglutaric acid are respectively measured;
mixing fluorine-silicon active intermediate sol C, isobornyl methacrylate, isooctyl acrylate, butyl acetate, 2-methyl-1-phenyl-2-propanol and a-ketoglutaric acid, and placing the mixture in a water bath at the temperature of 30 ℃ for stirring for 10min to obtain a pre-reaction solution;
conveying the pre-reaction liquid into an ultraviolet light reactor through a peristaltic pump, controlling the conveying flow to be 10mL/min, and controlling the reaction temperature to be 32 ℃ and the ultraviolet light irradiation wavelength to be 365nm; and collecting the reacted polymer solution at the outlet of the ultraviolet light reactor, adding the polymer solution into 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, mixing and diluting to obtain the organic fluorosilicone modified acrylic resin.
Example 4
(1) According to mass, 2 parts of vinyl triethoxysilane, 2 parts of vinyl methyl diethoxysilane, 2 parts of 1, 2-bis trimethoxy silicon-based ethane, 5 parts of 1H, 2H-perfluoro octyl trimethoxy silane, 55.5 parts of absolute ethyl alcohol, 15 parts of n-butyl alcohol, 10 parts of isobutanol, 5 parts of propylene glycol monomethyl ether, 1 part of methanesulfonic acid and 10 parts of deionized water are respectively measured;
mixing vinyl triethoxysilane, vinyl methyl diethoxysilane, 1, 2-bis trimethoxy silyl ethane, 1H, 2H-perfluoro octyl trimethoxy silane, adding into a reaction bottle filled with a mixed solution of absolute ethyl alcohol, n-butyl alcohol, isobutyl alcohol and propylene glycol monomethyl ether, stirring, and heating to 50 ℃; then uniformly dripping methanesulfonic acid and deionized water, controlling the dripping within 30min, continuously heating to 60 ℃, and preserving heat for 2h; distilling under reduced pressure, and removing about 50 parts of ethanol to obtain fluorine-silicon active intermediate sol D;
(2) In addition, according to mass, 10 parts of fluorine-silicon active intermediate sol D, 30 parts of methyl methacrylate, 30 parts of butyl acrylate, 27 parts of ethyl acetate, 100 parts of 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether and 1 part of 2-methyl-1-phenyl-2-propanol are respectively measured;
mixing fluorine-silicon active intermediate sol D, methyl methacrylate, butyl acrylate, ethyl acetate, 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether and 2-methyl-1-phenyl-2-propanol, and placing the mixture in a water bath at 30 ℃ to stir at constant temperature for 10min to obtain a pre-reaction liquid;
conveying the pre-reaction liquid into an ultraviolet light reactor through a peristaltic pump, controlling the conveying flow to be 15mL/min, the reaction temperature to be 32 ℃, and the ultraviolet light irradiation wavelength to be 365nm; and collecting the reacted polymer solution at the outlet of the ultraviolet light reactor, adding the polymer solution into 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, mixing and diluting to obtain the organic fluorosilicone modified acrylic resin.
Example 5
(1) According to mass, respectively weighing 4 parts of vinyl triethoxysilane, 1 part of 1, 2-bis trimethoxy silicon-based ethane, 5 parts of 1H, 2H-perfluoro octyl triethoxysilane, 47 parts of absolute ethyl alcohol, 30 parts of isopropanol, 3 parts of glacial acetic acid and 10 parts of deionized water;
mixing vinyl triethoxysilane, 1, 2-bis trimethoxy silicon-based ethane and 1H, 2H-perfluoro octyl triethoxysilane, adding into a reaction bottle filled with a mixed solution of absolute ethyl alcohol and isopropanol, stirring, and heating to 50 ℃; then glacial acetic acid and deionized water are dripped at a constant speed, dripping is completed within 30min, heating is continued to be carried out, and the temperature is kept for 2h; distilling under reduced pressure, and removing about 30 parts of ethanol to obtain fluorine-silicon active intermediate sol E;
(2) In addition, according to mass, 10 parts of fluorine-silicon active intermediate sol E, 15 parts of methyl methacrylate, 15 parts of hydroxyethyl methacrylate, 30 parts of butyl acrylate, 67 parts of ethyl acetate, 50 parts of 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, 10 parts of butyl acetate and 2 parts of 2-methyl-1-phenyl-2-propanol are respectively measured;
mixing fluorine-silicon active intermediate sol E, methyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, 27 parts of ethyl acetate and 2-methyl-1-phenyl-2-propanol, and placing the mixture in a water bath at a temperature of 40 ℃ for constant temperature stirring for 10min to obtain a pre-reaction solution;
conveying the pre-reaction liquid into an ultraviolet light reactor through a peristaltic pump, controlling the conveying flow to be 15mL/min, the reaction temperature to be 32 ℃, and the ultraviolet light irradiation wavelength to be 365nm; and collecting the reacted polymer solution at the outlet of the ultraviolet light reactor, adding the polymer solution into a mixed solution of 1, 2-tetrafluoroethyl 2, 2-trifluoroethyl ether, butyl acetate and 40 parts of ethyl acetate, and mixing and diluting to obtain the organic fluorosilicone modified acrylic resin.
Comparative example
Comparative example 1
Adding 20 parts of butyl acetate into a reaction bottle according to mass fraction, heating to 125 ℃, and refluxing at constant temperature; mixing 40 parts of methyl methacrylate, 10 parts of butyl acrylate, 5 parts of hydroxyethyl acrylate, 1 part of acrylic acid and 2 parts of dibenzoyl peroxide to obtain a mixed monomer;
dripping the mixed monomer into a reaction bottle with constant temperature of 125 ℃ for 2-2.5h, and ending the dripping; then preserving the heat at 125 ℃ for 2 hours, adding a mixed solution of 0.5 part of dibenzoyl peroxide and 5 parts of butyl acetate, and continuing the heat preservation reaction for 2 hours; after the reaction, cooling to 80 ℃, adding 16.5 parts of ethyl acetate, and stirring for 30min to obtain polyacrylate resin
< test example >
Sample: examples 1 to 5, comparative example 1
The resin materials prepared in examples 1 to 5 and comparative example 1 were prepared into a coating, and the coating was applied to the surface of a test wall to form a coating. The appearance of the coating was observed, and the performance parameters such as the water contact angle, the heat resistance and the weight loss degree of the coating were measured, and the results are summarized in the following table 1:
TABLE 1 coating Properties of different resin coatings
The heat-resistant weight reduction degree refers to the weight reduction percentage after being treated at 300 ℃ for 120min, namely, the smaller the heat-resistant weight reduction degree is, the better the heat resistance of the material is. The method for testing the heating weight loss degree comprises the following steps: the coating sample is dried for 24 hours at the room temperature of 25 ℃, then baked for 1 hour at 100 ℃, then baked for 1 hour at 200 ℃, weighed and recorded as the original weight M of the coating 0 The method comprises the steps of carrying out a first treatment on the surface of the Then the coating is put into a baking oven at 300 ℃ for baking for 120min, and is weighed and recorded as weight M after weight reduction 1 The method comprises the steps of carrying out a first treatment on the surface of the Calculate the heat-resistant weight loss degree= ((M) 0 -M 1 )/M 0 )*100％；
As can be seen from table 1 above:
compared with comparative example 1, the resin coatings prepared by examples 1-5 have water contact angles of more than 90 degrees, which means that the resin coating has better water resistance and stronger anti-fouling capability; the heat resistance and weight reduction degree obtained through measurement and calculation is obviously smaller, namely the heat resistance is strong; and the result of the visual water resistance and artificial aging resistance test can also show that the water resistance and stability are obviously stronger. In conclusion, the organic fluorosilicone modified acrylic resin provided by the invention can simultaneously have the performances of high water resistance, high heat resistance, strong stability and the like obviously superior to the traditional polyacrylate resin.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The organic fluorine-silicon modified acrylic resin is characterized by comprising fluorine-silicon reactive intermediate sol, methacrylate unsaturated monomer, acrylate monomer and initiator;
the preparation method of the fluorine-silicon active intermediate sol comprises the following steps:
mixing vinyl alkoxy silane, 1, 2-bis trimethoxy silicon-based ethane and fluorine-containing alkyl alkoxy silane, dissolving in alcohol solution, stirring and heating; and (3) dropwise adding an acid catalyst, heating, preserving heat, reacting for 1-5h, and removing the alcohol solution to obtain fluorine-silicon active intermediate sol.
2. The organofluorosilicone-modified acrylic resin according to claim 1, wherein the fluorine-silicon reactive intermediate sol is prepared from, by mass, 5 to 20 parts of vinyl alkoxysilane, 0.5 to 2 parts of 1, 2-bis trimethoxy silyl ethane, and 1 to 10 parts of fluorine-containing hydrocarbon-based alkoxysilane.
3. The organofluorosilicone-modified acrylic resin according to claim 2, wherein the amount of the alcohol solution is 63.6 to 85.8 parts by mass, and 30 to 50 parts of the alcohol solution is removed after the reaction.
4. The organofluorosilicone-modified acrylic resin according to claim 2, wherein the amount of the acid catalyst is 1 to 5 parts by mass, and 3 to 10 parts of water is also dropped when the acid catalyst is dropped.
5. The organofluorosilicone-modified acrylic resin according to any one of claims 1 to 4, wherein after being dissolved in an alcohol solution, it is heated to 40-50 ℃; after dropping the acid catalyst, heating to 50-60 ℃.
6. The organofluorosilicone modified acrylic resin according to claim 1, characterized by comprising 3 to 10 parts by mass of a fluoro-silicon reactive intermediate sol, 10 to 30 parts by mass of a methacrylate unsaturated monomer, 10 to 40 parts by mass of an acrylate monomer, and 1 to 3 parts by mass of an initiator.
7. The method for producing an organofluorosilicone-modified acrylic resin according to any one of claims 1 to 6, comprising the steps of:
s1, preparing a pre-reaction liquid:
mixing fluorine-silicon active intermediate sol with methacrylate unsaturated monomer, acrylate monomer, initiator and solvent, and stirring in a constant-temperature water bath to obtain a pre-reaction solution;
s2, preparing organic fluorine-silicon modified acrylic resin:
and (3) placing the pre-reaction liquid under the illumination with the wavelength of 350-380nm for reaction, and diluting to obtain the organic fluorosilicone modified acrylic resin.
8. The method for producing an organofluorosilicone-modified acrylic resin according to claim 7, wherein in step S1, the constant-temperature water bath temperature is 25 to 40℃and the stirring time is 5 to 15 minutes.
9. The method for producing an organofluorosilicone-modified acrylic resin according to claim 7 or 8, wherein in step S2, the reaction flow rate of the pre-reaction solution is controlled to be 10 to 20mL/min and the reaction temperature is controlled to be 25 to 40 ℃.
10. The method for producing an organofluorosilicone-modified acrylic resin according to claim 7, wherein in step S1, the solvent is used in an amount of 24 to 54 parts by mass; in step S2, 80-100 parts of solvent is used.
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| CN202311557679.XA Pending CN117417492A (en) | 2023-11-22 | 2023-11-22 | Organic fluorine-silicon modified acrylic resin and preparation method thereof |
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